Chapter 1

Structure Determines Properties

1.1
Atoms, Electrons, and Orbitals

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Atoms are composed of

Atomic Number and Mass Number

A

Protons
+

mass = 1.6726 X 10-27 kg

Neutrons
neutral
mass = 1.6750 X 10-27 kg

positively charged

Electrons

Atomic number (Z) = number of protons in nucleus

(this must also equal the number of electrons
in neutral atom)
Mass number (A) = sum of number of protons
+ neutrons in nucleus

negatively charged
mass = 9.1096 X 10-31 kg

Schrdinger Equation
Schrdinger combined the idea that an electron
has wave properties with classical equations
of wave motion to give a wave equation for the
energy of an electron in an atom.
Wave equation (Schrdinger equation) gives a
series of solutions called wave functions ( ).

Wave Functions
Only certain values of
Each

are allowed.

corresponds to a certain energy.

The probability of finding an electron at a

particular point with respect to the nucleus is
given by 2.
Each energy state corresponds to an orbital.

A boundary surface encloses the region

where the probability of finding an electron
is highon the order of 90-95%.

Figure 1.1 Probability distribution (

electron in a 1s orbital.

2)

for an

Figure 1.2 Boundary surfaces of a 1s orbital

and a 2s orbital.

Quantum Numbers
Each orbital is characterized by a unique
set of quantum numbers.
The principal quantum number n is a whole
number (integer) that specifies the shell and is
related to the energy of the orbital.
The angular momentum quantum number is
usually designated by a letter (s, p, d, f, etc)
and describes the shape of the orbital.

s Orbitals
s Orbitals are spherically symmetric.
The energy of an s orbital increases with the
number of nodal surfaces it has.
A nodal surface is a region where the probability
of finding an electron is zero.
A 1s orbital has no nodes; a 2s orbital has one;
a 3s orbital has two, etc.

The Pauli Exclusion Principle

First Period
Principal quantum number (n) = 1

No two electrons in the same atom can have

the same set of four quantum numbers. (n, , m, ms).
ml: magnetic quantum number
ms: electron spin quantum number

Hydrogen

Two electrons can occupy the same orbital

only when they have opposite spins.
There is a maximum of two electrons per orbital.

1s
H
He

Helium

Z=1

Z=2

1s 1

1s 2
2s

2p

p Orbitals

p Orbitals

p Orbitals are shaped like dumbells.

p Orbitals are shaped like dumbells.

Are not possible for n = 1.

Are possible for n = 2 and higher.

Are not possible for n = 1.

Are possible for n = 2 and higher.
There are three p orbitals for each value
of n (when n is greater than 1).

p Orbitals

p Orbitals

p Orbitals are shaped like dumbells.

p Orbitals are shaped like dumbells.

Are not possible for n = 1.

Are possible for n = 2 and higher.
There are three p orbitals for each value
of n (when n is greater than 1).

Are not possible for n = 1.

Are possible for n = 2 and higher.
There are three p orbitals for each value
of n (when n is greater than 1).

Second Period

Second Period

Principal quantum number (n) = 2

Z
Li 3
Be 4
B 5
C 6

1s

2s

Z
2p

Ne 10

1s

2s

2p

Ionic Bonding
An ionic bond is the force of electrostatic
attraction between oppositely charged ions.
1.2
Ionic Bonds
Na+ (cation)
Cl (anion)

Ionic Bonding
Ionic bonds are common in inorganic chemistry
but rare in organic chemistry.
Carbon shows less of a tendency to form cations
than metals do, and less of a tendency to form
anions than nonmetals.

The Lewis Model of Chemical Bonding

1.3
Covalent Bonds, Lewis Structures,
and the Octet Rule

Covalent Bonding in H2

In 1916 G. N. Lewis proposed that atoms

combine in order to achieve a more stable
electron configuration.

Two hydrogen atoms, each with 1 electron,

Maximum stability results when an atom

is isoelectronic with a noble gas.

can share those electrons in a covalent bond.

An electron pair that is shared between

two atoms constitutes a covalent bond.

H.

.H

H: H
Sharing the electron pair gives each hydrogen
an electron configuration analogous to helium.

Covalent Bonding in F2
Two fluorine atoms, each with 7 valence electrons,
..
..
. F:
: ..F .
..
can share those electrons in a covalent bond.
.. ..
: ..
F: ..
F:
Sharing the electron pair gives each fluorine an
electron configuration analogous to neon.

The Octet Rule

In forming compounds, atoms gain, lose, or
share electrons to give a stable electron
configuration characterized by 8 valence
electrons.
.. ..
: ..
F: ..
F:
The octet rule is the most useful in cases
involving covalent bonds to C, N, O, and F.

Example
Combine carbon (4 valence electrons) and
four fluorines (7 valence electrons each)
.
. C.
.

..
: ..
F.

to write a Lewis structure for CF4.

..
.. : ..F: ..
:
: ..F: C
.. : ..F
: ..F:

Example
It is common practice to represent a covalent
bond by a line. We can rewrite
..
.. : ..F: ..
:
: ..F: C
.. : ..F
: ..F:

..
: ..
F

as

The octet rule is satisfied for carbon and

each fluorine.

..
: F:
C

..
F:
..

: ..F:

Inorganic Examples
..
..
: O: : C : : O:
1.4
Double Bonds and Triple Bonds

..
:O

..
O:

N:

Carbon dioxide

H : C : :: N:

Hydrogen cyanide

Organic Examples
H
.. H
..
H: C: : C:H

H
Ethylene

H
C

H : C : :: C:H

Acetylene

1.5
Polar Covalent Bonds,
Electronegativity, and Bond Dipoles

Pauling Electronegativity Scale

Electronegativity
Electronegativity is a measure of the ability
of an element to attract electrons toward
itself when bonded to another element.
An electronegative element attracts electrons.
An electropositive element releases electrons.

Li

Be

1.0

1.5

2.0

2.5

3.0

3.5

4.0

Na

Mg

Al

Si

Cl

0.9

1.2

1.5

1.8

2.1

2.5

3.0

Electronegativity increases from left to right in the

periodic table.
Electronegativity decreases going down a group.

Generalization

Generalization

The greater the difference in electronegativity

between two bonded atoms; the more polar the
bond.
.. ..
: N N:
: ..
HH
F ..
F:

The greater the difference in electronegativity

between two bonded atoms; the more polar the
bond.

nonpolar bonds connect atoms of

the same electronegativity

..
F:
..

..
O
..

:O
..

polar bonds connect atoms of

different electronegativity

O
.. :

Electrostatic Potential Maps

Electrostatic Potential Maps

Electrostatic potential maps show the charge

distribution within a molecule.

Electrostatic potential maps show the charge

distribution within a molecule.

..
F:
..

..
F:
..

Transparent
surface

Solid
surface
Red is negative charge;
blue is positive.

Red is negative charge;

blue is positive.

Electrostatic Potential Maps

Electrostatic potential maps show the charge
distribution within a molecule.
..
H ..
H Li
F:

1.6
Formal Charge
Formal charge is the charge calculated for an
atom in a Lewis structure on the basis of an
equal sharing of bonded electron pairs.

Red is negative charge;

blue is positive.

Nitric acid

Nitric acid

Formal charge of H

..
O
..

Formal charge of H
..
O:
N
:O
.. :

We will calculate the formal charge for each

atom in this Lewis structure.

..
O
..

..
O:
N
:O
.. :

Hydrogen shares 2 electrons with oxygen.

Assign 1 electron to H and 1 to O.
A neutral hydrogen atom has 1 electron.
Therefore, the formal charge of H in nitric acid is 0.

Nitric acid

Nitric acid

Formal charge of O

..
O
..

Formal charge of O
..
O:
N

..
O
..

:O
.. :
Oxygen has 4 electrons in covalent bonds.
Assign 2 of these 4 electrons to O.
Oxygen has 2 unshared pairs. Assign all 4 of these
electrons to O.
Therefore, the total number of electrons assigned to O is
2 + 4 = 6.

Nitric acid

..
O:
N
:O
.. :

Electron count of O is 6.
A neutral oxygen has 6 electrons.
Therefore, the formal charge of O is 0.

Nitric acid

Formal charge of O

..
O
..

Formal charge of O
..
O:
N

..
O
..

:O
.. :
Electron count of O is 6 (4 electrons from
unshared pairs + half of 4 bonded electrons).
A neutral oxygen has 6 electrons.
Therefore, the formal charge of O is 0.

Nitric acid

..
O:
N
:O
.. :

Electron count of O is 7 (6 electrons from

unshared pairs + half of 2 bonded electrons).
A neutral oxygen has 6 electrons.
Therefore, the formal charge of O is -1.

Nitric acid
Formal charges

Formal charge of N

..
O
..

..
O:
N
:O
.. :

Electron count of N is 4 (half of 8 electrons in

covalent bonds).
A neutral nitrogen has 5 electrons.
Therefore, the formal charge of N is +1.

..
O
..

..
O:
N+

:O
.. :

A Lewis structure is not complete unless formal

charges (if any) are shown.

Formal Charge

Formal Charge

An arithmetic formula for calculating formal charge.

"Electron counts" and formal

charges in NH4+ and BF4-

Formal charge =

Electron Count =

Group number
- Electron Count
in periodic table
number of
unshared electrons

1
H

+
H

: ..F:

(Number shared
electrons)

..
: F:
..
..
: ..
F:
F B ..

Constitution
The order in which the atoms of a
molecule are connected is called its
constitution or connectivity.

1.7
Structural Formulas of Organic Molecules

The constitution of a molecule must

be determined in order to write a
Lewis structure.

Constitutional isomers
Isomers are different compounds that
have the same molecular formula.
Constitutional isomers are isomers
that differ in the order in which the
atoms are connected.
Constitutional isomers are also called
structural isomers.

Examples of constitutional isomers

Ethanol

..
O
..

H
H

C
H

..
O
..

H
C

Dimethyl ether

Both have the molecular formula C2H6O but the

atoms are connected in a different order.

Examples of constitutional isomers

H
H

C
H

..
O:

N+

:O
.. :

Nitromethane

..
O
..

N
..

..
O:

1.8
Resonance

H
Methyl nitrite

Both have the molecular formula CH3NO2 but

the atoms are connected in a different order.

Resonance
Two or more Lewis structures may be
written for certain compounds (or ions).

Table 1.6 Introduction to the Rules of Resonance

Step 1:
The connectivity must be the same in all
resonance structures.

Recall from Table 1.6

Example:
The Lewis formulas below are not
resonance forms of the same compound.

Table 1.6 Introduction to the Rules of Resonance

Table 1.6 Introduction to the Rules of Resonance

Step 2:
Each contributing structure must have
the same number of electrons and same
net charge.
Example:
All structures have 18 electrons and a
net charge of 0.

Step 3:
Calculate formal charges on the first
structure.
Example:
None of the atoms possess a formal
charge in this Lewis structure.

Table 1.6 Introduction to the Rules of Resonance

Resonance Structures of Methyl Nitrite

Step 4:

same atomic positions

Calculate formal charges on the second
and third structures.

differ in electron positions

H

Example:
These structures have formal charges;
these are less stable Lewis structures.

..
O
..

N
..

..
O:

+
O
..

N
..

..
O
.. :

more stable
Lewis
structure

Resonance Structures of Methyl Nitrite

less stable
Lewis
structure

Why Write Resonance Structures?

same atomic positions

differ in electron positions
H
H

..
O
..

N
..

Electrons in molecules are often delocalized

between two or more atoms.

..
O:

+
O
..

N
..

more stable
Lewis
structure

less stable
Lewis
structure

..
O
.. :

Electrons in a single Lewis structure are

assigned to specific atoms-a single Lewis structure
is insufficient to show electron delocalization.
Composite of resonance forms more accurately
depicts electron distribution.

Example

Example

Ozone (O3)
Lewis structure of
ozone shows one
double bond and
one single bond

Ozone (O3)

Expect: one short bond and one

long bond
Reality: bonds are of equal length
(128 pm)

+
O

Lewis structure of
ozone shows one
double bond and
one single bond

+
O

Resonance:

+
O

+
O

Example
Ozone (O3)
Electrostatic potential
map shows both end
oxygens are equivalent
with respect to negative
charge. Middle oxygen
is positive.
+
O

1.9
Writing Organic Structures

+
O

Bond-line formulas

Condensed structural formulas

Lewis structures in which many (or all)
covalent bonds and electron pairs are
omitted.
H H H
H

H : O: H

can be condensed to:

CH3CHCH3 or (CH3)2CHOH

OH

CH3CH2CH2CH3 is shown as
CH3CH2CH2CH2OH is shown as
Omit atom symbols. Represent
structure by showing bonds between
carbons and atoms other than
hydrogen.
Atoms other than carbon and hydrogen
are called heteroatoms.

Bond-line formulas
H3C

Cl
C

H2C

CH2

H2C

CH2

Cl
is shown as

simplifies to

1.10
The Shapes of Some Simple Molecules

OH

Valence Shell Electron Pair Repulsions

The most stable arrangement of groups

attached to a central atom is the one that has
the maximum separation of electron pairs
(bonded or nonbonded).

Table 1.7 Methane

tetrahedral geometry
HCH angle = 109.5

Table 1.7 Methane

Table 1.7 Water

tetrahedral geometry
each HCH angle = 109.5

bent geometry
HOH angle = 105

H
H
O

..
but notice the tetrahedral arrangement
of electron pairs

Table 1.7 Ammonia

Table 1.7 Boron Trifluoride

trigonal pyramidal geometry

HNH angle = 107

FBF angle = 120

trigonal planar geometry
allows for maximum separation
of three electron pairs

H
H

H
but notice the tetrahedral arrangement
of electron pairs

Multiple Bonds

Table 1.7: Formaldehyde

Four-electron double bonds and six-electron

triple bonds are considered to be similar to a
two-electron single bond in terms of their spatial
requirements.

HCH and HCO

angles are close to 120
trigonal planar geometry.

H
C

Table 1.7 Carbon Dioxide

OCO angle = 180
linear geometry
1.11
Molecular Dipole Moments

Dipole Moment
A substance possesses a dipole moment
if its centers of positive and negative charge
do not coincide.
=exd
(expressed in Debye units)

not polar

Dipole Moment
A substance possesses a dipole moment
if its centers of positive and negative charge
do not coincide.
=exd
(expressed in Debye units)

+
polar

Molecular Dipole Moments

-

molecule must have polar bonds

Molecular Dipole Moments

Carbon dioxide has no dipole moment;

=0D

necessary, but not sufficient

need to know molecular shape
because individual bond dipoles can cancel

Figure 1.7

Figure 1.7

Resultant of these

Resultant of these

two bond dipoles is

two bond dipoles is

=0D
Carbon tetrachloride

Dichloromethane

=0D

= 1.62 D

Carbon tetrachloride has no dipole

moment because all of the individual
bond dipoles cancel.

Figure 1.7

Resultant of these

Resultant of these

two bond dipoles is

two bond dipoles is

= 1.62 D
The individual bond dipoles do not
cancel in dichloromethane; it has
a dipole moment.

1.12
Curved Arrows and Chemical
Reactions

Curved Arrows
Curved arrows are used to track the flow of
electrons in chemical reactions.

Curved Arrows
Consider the dissociation of H2CO3:

The arrow begins where the electrons were

originally and points to where they end up
Consider the reaction shown below which
shows the dissociation of A-B

Curved Arrows
Many reactions involve both bond breaking
and formation. More than one arrow may be
required.

1.13
Acids and Bases:
The Arrhenius View

Definitions
Arrhenius
An acid ionizes in water to give protons. A
base ionizes in water to give hydroxide ions.
Brnsted-Lowry
An acid is a proton donor. A base is a proton
acceptor.
Lewis
An acid is an electron pair acceptor. A base
is an electron pair donor.

Arrhenius Acids and Bases

An acid is a substance that ionizes to give
protons when dissolved in water.
H

.
H + + .A

A base is a substance that ionizes to give

hydroxide ions when dissolved in water.
M

..
OH
..

. ..
M+ + . OH
..

Acid Strength is Measured by pKa

Arrhenius Acids and Bases

Strong acids dissociate completely in water.
Weak acids dissociate only partially.
H

.
H + + .A

Ka =

Strong bases dissociate completely in water.

Weak bases dissociate only partially.
M

..
OH
..

.
H + + .A

[H+][A]
[HA]

pKa = log10Ka

. ..
M+ + . OH
..

A Brnsted Acid-Base Reaction

A proton is transferred from the acid to the
base.

1.14
Acids and Bases:
The Brnsted-Lowry View

B .. + H A

Brnsted-Lowry definition
an acid is a proton donor
a base is a proton acceptor

A Brnsted Acid-Base Reaction

base

base

acid

+
B

H + .. A

conjugate
acid

conjugate
base

H + .. A

acid

Proton Transfer from HBr to Water

A proton is transferred from the acid to the

base.
B .. + H A

+
B

hydronium ion
H
..
..
.. O ..
+ H Br
..
H
base

acid

.. O+ H
. .. ..
+ . Br
..
H
conjugate conjugate
acid
base

Equilibrium Constant for Proton Transfer

H
..
.. O .. + H Br ..
..
H
Ka =

H
.. .
.. O+ H + .. Br
.. .
H
[H3O+][Br]

Equilibrium Constant for Proton Transfer

H
..
.. O .. + H Br ..
..
H
Ka =

[HBr]

Takes the same form as for Arrhenius Ka, but

H3O+ replaces H+. H3O+ and H+ are
considered equivalent, and there is no
difference in Ka values for Arrhenius and
Brnsted acidity.

H
.. N

base

acid

[HBr]

pKa = log10 Ka

Dissociation Constants (pKa) of Acids*

Water as a Brnsted Acid

H
..
.. N..
+ H OH
..
H

H
.. .
.. O+ H + .. Br
.. .
H
[H3O+][Br]

stronger
acid

Acid

..
H + .. OH
..

conjugate conjugate
acid
base

Conj. Base

-10.4

HI

pKa

HBr

-5.8

Br

H2SO4

-4.8

HSO4

HCl

-3.9

Cl

-1.7

H2O

weaker
acid

H3O

strong acids are stronger than hydronium ion

Important Generalization!
stronger
acid

Acid

-10.4

HI

Conj. Base
I

-5.8

Br

H2SO4

-4.8

HSO4

H3O

-3.9
-1.7

stronger
acid

HBr

HCl
weaker
acid

pKa

Dissociation Constants (pKa) of Acids*

Cl

H2O

The stronger the acid, the weaker the conjugate base.

weaker
acid

Acid

pKa

Conj. Base

H3 O

1.7

H2O

HF

3.5

CH3CO2H

4.6

CH3CO2

+
NH4

9.2

NH3

H2 O

15.7

HO

weak acids are weaker than hydronium ion

Dissociation Constants (pKa) of Acids*

Acid

pKa

Conj. Base

CH3OH

15.2

CH3O

H2O

15.7

HO

CH3CH2OH

~16

CH3CH2O

(CH3)2CHOH

~17

(CH3)2CHO

~18

(CH3)3COH

Dissociation Constants (pKa) of Acids*

Acid

pKa

Conj. Base

NH3

~36

NH2

(CH3)2NH

~36

(CH3)2N

(CH3)3CO

ammonia and amines are very weak acids;

their conjugate bases are very strong bases

Table: 1.8

Dissociation Constants (pKa) of Acids*

HC
H

pKa

CH
H

26

H
H2C

43

H
CH2

CH3CH3

Conj. Base
HC

H
H

62

H
45

alcohols resemble water in acidity; their conjugate

bases are comparable to hydroxide ion in basicity

Acid

H2C

CH

CH3CH2

Most hydrocarbons are extremely weak acids.

Tab. 1.8(Contd.)

1.15
What Happened to pKb?

H
Example

About pKa and pKb

A separate basicity constant Kb is not
necessary.
Because of the conjugate relationships in the
Brnsted-Lowry approach, we can examine
acid-base reactions by relying exclusively on
pKa values.

H
N
N

Which is the stronger base, ammonia (left) or

pyridine (right)?
Recall that the stronger the acid, the weaker
the conjugate base.
Therefore, the stronger base is the conjugate
of the weaker acid.
Look up the pKa values of the conjugate acids
of ammonia and pyridine in Table 1.8.

Example
H
H

+
N

pKa = 9.3

weaker acid

1.16
How Structure Affects Acid Strength

+
N
H

pKa = 5.2

stronger acid

Therefore, ammonia is a
stronger base than pyridine

The Main Ways Structure Affects Acid Strength

The strength of the bond to the atom from
which the proton is lost

Bond Strength
Bond strength is controlling factor when
comparing acidity of hydrogen halides.

The electronegativity of the atom from which

the proton is lost
Electron delocalization in the conjugate base

pKa

HF

HCl

HBr

HI

3.1

-3.9

-5.8

-10.4

weakest acid
strongest HX bond

strongest acid
weakest HX bond

Bond Strength
Recall that bond strength decreases in a group
in going down the periodic table.
Generalization: Bond strength is most
important factor when considering acidity of
protons bonded to atoms in same group of
periodic table (as in HF, HCl, HBr, and HI).

The Main Ways Structure Affects Acid Strength

The strength of the bond to the atom from
which the proton is lost
The electronegativity of the atom from which
the proton is lost
Electron delocalization in the conjugate base

Another example: H2S (pKa = 7.0) is a

stronger acid than H2O (pKa = 15.7).

Electronegativity

Electronegativity

Electronegativity is controlling factor when

comparing acidity of protons bonded to atoms
in the same row of the periodic table.
pKa

CH4

NH3

H2O

HF

60

36

15.7

3.1

weakest acid
least electronegative

Electronegativity
R
.. O .. + H A

R
.. O+ H + .. A

The equilibrium becomes more favorable as A

becomes better able to bear a negative charge.
Another way of looking at it is that H becomes
more positive as the atom to which it is
attached becomes more electronegative.

strongest acid
most electronegative

Bond Strength Versus Electronegativity

Bond strength is more important when
comparing acids in which the proton that is lost
is bonded to atoms in the same group of the
periodic table.
Electronegativity is more important when
comparing acids in which the proton that is lost
is bonded to atoms in the same row of the
periodic table.

Acidity of Alcohols

Acidity of Alcohols
pKa

In many acids
the acidic proton
is bonded to
oxygen.
Alcohols (ROH)
resemble water
(HOH) in their
acidity.

HOH

15.7

CH3OH

15.2

CH3CH2OH

16

(CH3)2CHOH

17

(CH3)3COH

18

Electronegative substituents can increase the

acidity of alcohols by drawing electrons away
from the OH group.

pKa

CH3CH2OH

CF3CH2OH

16
weaker

11.3
stronger

Electrostatic Potential Maps

Inductive Effect

The greater positive character of the proton of

the OH group of CF3CH2OH compared to
CH3CH2OH is apparent in the more blue color
in its electrostatic potential map.

The greater acidity of CF3CH2OH compared to

CH3CH2OH is an example of an inductive effect.
Inductive effects arise by polarization of the
electron distribution in the bonds between
atoms.

Another Example of the Inductive Effect

CH3CH2OH

CF3CH2OH

The Main Ways Structure Affects Acid Strength

The strength of the bond to the atom from
which the proton is lost

O
CH3C O H
pKa

4.7
weaker

The electronegativity of the atom from which

the proton is lost

O
CF3C

O H

0.50
stronger

Electron delocalization in the conjugate base

Electron Delocalization

Nitric Acid

R
.. O .. + H A

R
.. O+ H + .. A

O + H

N+

O

pKa = -1.4

Ionization becomes more favorable if electron

delocalization increases in going from right to
left in the equation.

H
O+ H

Resonance is a convenient way to show

electron delocalization.

O
N+

O

Nitric Acid

Nitric Acid

Negative charge is
shared equally by all
three oxygens.

N+
O

Nitrate ion is stabilized by

electron delocalization.

O
N+

O

N+

O

O
N+

O

Acetic Acid

Acetic Acid

O
O + H

H
pKa = 4.7

CH3

H
O+ H

O
Acetate ion is stabilized by
electron delocalization.

C
CH3

O
C
CH3

Acetic Acid
Negative charge is
shared equally by
both oxygens.

O

O

1.17
Acid-Base Equilibria

CH3

CH3

Generalization

Example of a Strong Acid

The equilibrium in an acid-base reaction is

favorable if the stronger acid is on the left and
the weaker acid is on the right.
Stronger acid + Stronger base

Weaker acid + Weaker base

H
..
.. O .. + H Br ..
..
H

H
.. .
.. O+ H + .. Br
.. .
H

pKa = -5.8

pKa = -1.7

stronger acid

weaker acid

The equilibrium lies to the side of

the weaker acid. (To the right)

Important Points

Example of a Weak acid

A strong acid is one that is stronger than H3O+.

A weak acid is one that is weaker than H3O+.

OCCH

A strong base is one that is stronger than HO.

A weak base is one that is weaker than HO.

O + HOCCH

3

pKa = 4.7

+
OH
+

H
pKa = -1.7

weaker acid
stronger acid
The equilibrium lies to the side of
the weaker acid. (To the left)

The strongest acid present in significant

quantities when a strong acid is dissolved in
water is H3O+.
The strongest acid present in significant
quantities when a weak acid is dissolved in
water is the weak acid itself.

Predicting the Direction of Acid-Base Reactions

Predicting the Direction of Acid-Base Reactions

O

HO + HOC6H5

HOH + OC6H5

pKa = 10

Water
pKa = 15.7

stronger acid

weaker acid

Phenol

The equilibrium lies to the side of the weaker

acid. (To the right) Phenol is converted to
phenoxide ion by reaction with NaOH.

HOCO + HOC6H5

Phenol
pKa = 10
weaker acid

HOCOH +

OC H

6 5

Carbonic acid
pKa = 6.4
stronger acid

The equilibrium lies to the side of the weaker

acid. (To the left) Phenol is not converted to
phenoxide ion by reaction with NaHCO3.

Definitions

1.18
Lewis Acids and Lewis Bases

Arrhenius
An acid ionizes in water to give protons. A
base ionizes in water to give hydroxide ions.
Brnsted-Lowry
An acid is a proton donor. A base is a proton
acceptor.
Lewis
An acid is an electron pair acceptor. A base
is an electron pair donor.

Lewis Acid-Lewis Base Reactions

The Lewis acid and the Lewis base can be
either a neutral molecule or an ion.
Lewis acid

Example: Two Neutral Molecules

CH2CH3
F3B

+ Lewis base

CH2CH3

A+

AB

AB

A+

AB +

AB +

Lewis acid

F3B

CH2CH3
+
O
CH2CH3

Lewis base

Product is a stable substance. It is a liquid with

a boiling point of 126C. Of the two reactants,
BF3 is a gas and CH3CH2OCH2CH3 is a liquid
with a boiling point of 34C.

Example: Ion + Neutral Molecule

HO +

Lewis base

H3CBr

HOCH3

Example: Ion + Neutral Molecule

+

Br

Lewis acid

HBr

Lewis base

Reaction is classified as a substitution. But notice

how much it resembles a Brnsted acid-base reaction.

HO +

HO +

HOH

Br

H3CBr

HOCH3

Br

Lewis acid

Brnsted acid-base reactions are a subcategory of

Lewis acid-Lewis base reactions.

HO +

HBr

HOH

Br